Cementitious material.



UNITED STATES PATENT OFFICE.

HENRY S. SPACKMAN, OE ARDMORE, PENNSYLVANIA, AND ELLIS W. LAZELL, OF

' WILMINGTON, DELAWARE; SAID'LAZELL ASSIGNOR TO SAID SPAGKMAN.

CEMENTITIOUS MATERIAL.

No Drawing.

To all whom it may c0ncern.

Be it known that we, HENRY S. SPAoK- MAN, a resident of Ardmore, Montgomery county, State of Pennsylvania, and ELLIS W. LAZELL, formerly a resident of the city and county of Philadelphia, State of-Pennsylvania, and now a resident of Wilmington, county of Newcastle, and State of Delaware, have made a certain new and useful Inven tion Relating to Cementitious Materials, of which the following is a specification.

This invention relates to cementitious, that is to say, plastic materials or compositions, such as plasters, hydraulic and other cements, comprising incorporated, calcium aluminates or equivalent strength accelerating material, and to such energizing material and to its preparation and incorporation'with other cementitious material comprising available lime or similar earthy alkali materlal, to accelerate the cementitious or binding properties thereof.

Calcium aluminum compounds of substantially the composition of calcium aluminates which contain from one to three molecules of lime to one of alumina may be prepared by calcining finely ground lime and bauxite or other aluminum compound, such as kaolin or high aluminum clays, theburned material when lime and bauxite are employed being sinterecl and giving a very quick initial set when ground and moistened with water. Calciumaluminate material, such as is formed preferably by thoroughly calcining or sinterlng a relatively small propor, tion of available lime as compared with the available alumina present, attains its initial set after a relatively long period and its final set in a relatively short time thereafter. Such low-lime calcium aluminate cement materials, besides being themselves more or less strongly hydraulic and cement-itious, exert a valuable energizing action on cementitious material comprising lime or other earthy alkali material (such as magnesia, baryta, strontia, or other material capable of combining with cooperating sili'cious material and calcium aluminate strength ac-. celerating material). When incorporated for example with natural cements their cementitious or binding properties are eccelerated so as to greatly increase the early sand strengths of the mixed material in the same general way as when using the high lime calcium aluminate material formed by the union of one to three or more molecular Specification of Letters Patent.

Patented June is, 1912.

Application filed July 11, 1911. Serial No. 637,903.

weights of lime to one of alumina; while at the same time it is easier to prevent the composition having an undesirably quick initial set. Such low-lime calcium aluminates may preferably be prepared by uniting suitably proportioned mixtures of finely ground lime, magnesia or other earthy alkali with bauxite or other material rich inalumina or alumina-like material, the components being incorporated in such proportions that the lime for example is present to of grinding may be still further heated to complete fusion as in a blast furnace after which it may be advantageously granulated in water or otherwise before being ground, the higher the tem erature of union the slower as 'a genera thing is the setting action. It is of course understood that iron oxid or similar material may be .used in some cases to replace to some extent at least the alumina in this accelerating material,:

and that other earthy alkali material, such as magnesia and so forth, may be substituted for part at least of the lime combined, that is, more or less closely united therewith, such calcium aluminates and equivalent or substitute accelerating or energizing material being designated earthy alkali, strength accelerating compounds of aluminalike material.

Suitable proportions of calcium aluminate or similar strength accelerating mate rial andalso if desired of controlling material to assist in efi'ecting the desired quickness of set and increase of strength may be prepared and incorporated at any time before utilization with the independently cementitious material comprising oxids, hydrates or otherwise available lime or similarly acting earthy alkali material combining or capable of combining with the aluminous accelerating material and cooperatingsilicious material which may also be present if desired; suitable controlling material such as sulfate of lime, sulfuric acid and in the case of plastic compositions, glue, starch, etc, may also be uniformly incorporated. The aluminous accelerating material preferably in finely divided condition may be prepared and incorporated before or after the gaging of the cementitious material or may be dissolved or incorporated in thegaging water; preferably, however, the strength accelerating and controlling material may be uniformly. incorporated with the independently cementitious material so as to form a finely divided material convenient for transportation and utilization since it becomes immediately efi'ective when water is added thereto.

Hydraulic cements having high strengths at early periods and comprising large proportions of such calcium aluminate cement material or the like, with cooperating lime or equivalent earthy alkali material in connection with cooperating silicious material and controlling material if desired, may be prepared by having present a sufficient proportion of slow-setting calcium aluminate to give the desired setting time to the compositions, which in many cases have sand strengths at early periods considerably in excess of the standard Portland cement requirements; many mixtures of slow-setting low-limed calcium aluminate with higher limed, quick setting calcium aluminate produce cements having much greater strength than ordinary Portland cements and partakingof the slow-setting qualities of low lime calcium aluminates. An illustrative composition of this character may be pre pared by making a finely divided mixture of low lime, slow-setting, hydraulic, highly cementitious, calcium alu-minate produced by thorough calcination and having the following approximate analysis:

Silica (SiO 2.12% Alumina (A1 0 65.32 Iron (F6 0 12.16 Lime (CaO) 20. 94 Magnesia (MgO) .44 Volatile matter None.

and an equal proportion of a diversely prepared calcium aluminate higher in lime,hav-

ing an initial set of five minutes and a final setof seven minutes and containing:

This composite hydraulic composition when tested according to the' standard methods adopted by the American Society of Civil Engineers and prescribed by the American Society for Testing Materials in conjunction with the standard specifications for testing of Portland'cements, gave the following results:

Setting time: Gihnores needle per cent. of water, 28; initial set, 5 hrs.; final set, 5 hrs. 30 min.; constancy of volume: 0. K.

Tensile test: 1 part mixture, 3 parts sand; kept in water after 24 hours.

24 hours. 7 days. 28 days. 3 months.

Lbs. Lbs. Lbs. Lbs.

Average 3&5 500 512 695 Tensile test: same 1 to 3 mixture, kept in air.

7 days. 28 days. 3 months.

Lbs. Lbs. Lbs.

Average e 5 0 7 rials, or if desired suitable proportions of finely divided, inert materials or stretchers, such as finely ground silica which may be used up to about twice the amount of the combined calcium aluminate material where hydraulic, slow setting the cement is to be used for ordinary purposes. An illustrative composition of this character may be prepared by mixing fifty parts of finely ground sand, twenty-five parts of the above slow-setting, lowelime calcium aluminate, twenty-five parts of the higher lime, quick setting calcium aluminate, all being ground to such fineness as to pass the #100 mesh sieve. This cement when tested in the usual manner for Portland cement with the addition of three parts, by weight, of standard Ottawa sand, gave the following results:

Setting time: initial set, 4 hrs. 35 minutes; final set, 6 hrs. 39 minutes.

Tensile tests: 2st hours, 168 lbs; 7 days, 198 lbs.; 28 days, 240 lbs. i

A similar composition using inert stretchers was made of one half of this slow-setting, low-lime calcium aluminate, one-half finely ground sand. This when tested in the manner usual for Portland cement with the addition of threeparts, by weight, of 'stand ard Ottawa sand, gave the following physical tests:

Tensiletestsz24 hours, 83 lbs; 7 days,

' 198 lbs.; 28 days, 332 lbs. The low-lime, slow-setting calcium aluminate cement materials when used alone have a longer period of plasticity, not acquiring their lnitlal set as a rule under ten hours but develop very high strength shortly afterward. An illustrative example, when tested in the usual manner for Portland cement did not acquire its initial set under ten hours yet when tested one part cement to. three parts sand, by weight, gave at 24: hours 233 pounds, and at seven days 435 pounds. Such low-lime,slow-setting calcium aluminate cement material and also composite strength accelerating material comprising the same in admixture with high-lime, quick setting calcium aluminate materials may of course be used when incorporated with suitable proportions of lime. Such slow-setting, strength accelerating material is of course desirable for incorporation with quick-set ting natural cements or other quick-setting cementitious materials, it being possible to incorporate considerably larger proportions ciumaluminate, two per cent. of calcium sulfate being present in-all cases; it being, of course, understood that such highly cemen- 'titious material produced .by the incorporation of the 'aluminates fulfills the constant volume and sand strength requirements for standard Portland cement.

' I Natural ce- Natural ce- N utural cement with 10% ment with 1 0% ment. slow setting higher lime aluminate. aluminate.

Initial set 1 hr. 35 min. 3 hrs. 14 min; 20 minutes. Final set 2 hrs. 40 min. 4111's.. min. 30 minutes.

Tensile strengths: 1 part cement, 8 parts sund- 24 hrs No strength. 175 lbs. 150 lbs. 7 days 95 lbs. 288 lbs. 200 lbs. 28 days 156 lbs. 368 lbs. 2'10 lbs.

Several illustrative examples of slow-setting, hydraulic, aluminous, strength accelermaterials containing considerable silica and which were completely fused during their manufacture so as to have comparatively slight strengths at' early -per1ods whenuse'd alone or in the absence of availusingv'iron orescontaining approximately fourteen per cent. of alumina, these alumiable lime were produced in a blast furnace nous slags had the following approximate analyses;

- No. 1 No. 2

Silica (SiO,) 29.12% 31. 96% Alumina (A1 0 :34.28' 28.94 Iron (Fe) 2.40 2. 39. 1 Lime (CaO) 29. 82 28. 46. Magnesia (MgO) 2.32 3.78

The following comparative test shows the result of incorporating ten percent. ofthe strength accelerating material indicated in the sec'ondanalysis given above with the fol; lowing natural cement in comparisonwith a similar incorporation of quick-setting, Y

7 higher lime aluminate, strength accelerating material with the same natural cement.

Natural ce- I Natural ce- Natural cegg m z m ment with 10% ment, 10w higher lime aluminate. alummate' 1 Initial set 1 hr. 35 min. 6 hrs. 9 min. 20 minutes. Final set 2 hrs. 40 min. 8hrs. 30 minutes.' Tensiletest: 1 part i cement, 3 parts sand.

7 days 95 lbs. 230 lbs. 200 lbs. 28 days 156 lbs. 385 lbs. 270 lbs.

The fused calcium aluminate strength ac celerat-ing materia having the second analysis given above, when mixed with an equal proportion of low-lime calcined calcium aluminate material such as referred to in connection with the first analysis given. in this application, produced a slow-setting highly cementitious material -which gave when tested in the ordinary way for cement with three parts of sand the following tensile strengths: 180 pounds at seven days,

490 pounds at twenty-eight days and 530 pounds at three months. alumina, high silica material can also be advantageously used either alone or in conjunction with low-lime, slow-setting calcium aluminate as an addition to independently cemcntitious material, such as lime. Similar composite aluminate strength accelerat: ing materials produce hydraulic highly cementit'ious material when incorporated with considerable proportions offinely Iground' inert materials, slliciousstretchers or coop- Such high erating' silicious and other materials and may be advantageously incorporated with natural cements, for example: a mixture containing ten parts fused calcium aluminate containing considerable proportions of silica, analysis #2, two parts plaster, eighty-eight parts natural cement, when an initial setting time of 6 hours 9 minutes and a final setting time of .8 hours; and

.'hardness' and strength of 'plastie that is to when tested in water with three parts. of

sand had 230 pounds tensile strength at seven days and 335 pounds at twenty-eight days.

Such fused aluminous and other cal: ciumjaluminate' strength accelerating materialmay be advantageously incorporated in comparatively small proportions with suitable plaster 1 or -cementitious material such as lime or similar alkali material, these compositions comprising from about one to ten per cent. of incorporated alumina and having greatly increased setting spreading and sand-carrying properties. Such suitable illustrative plaster compositions may be prepared by incorporating five to twenty er cent-of such fused calcium aluminate strength acceleratin cement material with ordinary hydrated ime, connection, if desired, with suitable stretcher-s or other 1n gradients. The following table shows the tensile strengths .when tested with four parts of commercial sand,of hydrated lime with: which ten and fifteen per cent. of this fused 'aluminousmaterial containing a considerable amount of silica had been incorporated:

- Hydratedlime .Hydrated lime with 10% with 15% alumlnate. alum nate.

' 35m 381135. ys.... B6lbs. 681bs. 28days 't'fi lbs. 781135.

, Various proportions of-the higher lime aluminons accelerator which may be pro.- duced bythe calcination of about one to three molecular" weights of lime to one of alumina ;may he added to slaked 'lime so as to secure thedesired uickness of set and increase of. strength 0 the material, A good composition for use as commercial wall plaster 'may be prepaned by'incor 0- rating such an amount of aluminous acce erating material with lime] or other plaster 'Inaterial asto increase its alumina content from one toten per cent, the ingredients beingj preferably ethoroughly mixed .by-

grinding them together ori-otherwisa' The one to ten percent. it being alsodesirable to add-from one to five per cent. ofplaster ofParis to control the setting. Ade'sirable composition for general use as wallplaster may be prepared by incorporating eightysix parts of dry hydrated lime, zten parts of calcium; alummate accelerating material containing apprcximately40% of alumina, two parts of plaster of Paris and two parts of infusorial earth. This material, when, the components were thoroughly incorporated and finely ground together so "that ninety-five percent. passed through a one hundred mesh sieve had an initial setting .time of about four hours .and was completely set in about fifteen hours according .to the indications" of the standard Vicat sand in -air gave the following high tensile strengths: at seven days'l25 pounds per square inch and at twenty-eight days 151' pounds per square inch.

Having described the invention in this case,\wh1ch is a continuation, that is, contains subject matter taken from our copendlso ing applications filed September 27, 1907,

as Serial No. 394,916, and renewed November 22,1909, as Serial 'No. 529,294, filed July 3, 1908, as Serial No. 441,731, and filed March 29, 1909 as Serial No. 486,432,'in connection with a number of illustrative ingredients, proportions,

formulas, and methods of preparation, to the details of which disclosure the invention is not of course to be limited, what is claimed as new and what is desired to be secured by Letters Patent is set forth in the appended claims:

1. The hydraulic quick setting highly cementitious cement material capable of developing and accelerating the cementitious properties and early strengths of cooperat- 'ing cementitious material containin available lime when incorporated therewlthand formed by calcining a mixture of lime and bauxite, the lime being present in amounts slightly'more than sufiicient to be capable of combining in, dicalcicproportions with the alumina in addition to combining with operating materials.

. 3. The cement materialcapable of developing or accelerating the cementitious properties and early strengths of cooperat ingcementitious material containing available lime when incorporated therewith and formed uniting at high heat a mixture of liziie and material rich in alumina, the

lime being present in amounts slightly more than sufficient to be capable of'combining in dicalcic proportions with the alumina in present in'amounts slightly more than suiiicie'nt to be capable of combining in dicalcic proportions with the alumina in addition to combining with any silica and other coaddition to combining .with any silica or other cooperating materials.

4. The cement material capable of developing or accelerating the cementitious properties and early strengths of cooperatingcementitious material containing avail- .able lime when incorporated therewith and formed by uniting at high heat a mixture of lime and material rich in alumina, the lime being present in amounts more than sufficient to be capable of combining in dicalcic proportions with the alumina in addition to combining with any silica and other coiiperating materials.

.5. The cement material capable of developing or accelerating the cementitious properties of cooperating cementitious materials containing available lime when incorporated therewith and formed by uniting a mixture of lime and material rich in alumina, the lime being present in amounts more than sufiicient to be capable of combining in dicalcic proportions with the alumina in addition to combining with any silica and other cooperating materials.

6. The calcium aluminate cement material capable of developing andaccelerating the cementitious properties and early strengths 'of cooperating cementitious material containing available lime when incorporated therewith and being relatively high in alumina and low in silica and formed by uniting at high heat a mixture of lime and aluminous material containing iron and silica, the lime being present inamounts more than sufiicient to be capable of combining in dicalcic proportions with the I alumina in addition to combining with any silica and other cooperating materials.

7. The calcium aluminate cement material capable of developing and accelerating the cementitious properties and early strengths of cooperating cementitious material'containing available lime when incorporated therewith and formed by uniting at high heat a mixture of lime and bauxite, the lime being present in amounts more than suflicient to be capable of combining in dicalcic proportions with the alumina in ad- 'dition to combining with any silica and other cooperating materials.

8. The cement material capable of developing or accelerating the cementitious properties of cooperating cementitious material containing available lime when incorporated therewith and formed by uniting a mixture of lime and bauxite, the lime being present in said cement material in amounts more than suflicient to be capable of combining in dicalcic proportions with the alumina in addition to combining with any silica and other cooperating materials.

9. The highlime, cement material capable of developing or accelerating the cementitious properties" of cooperatlng cementitious material containing large proportions of available lime when incorporated therewith and formed by uniting at high heat lime and high aluminous material.

10. The high lime, cement material capable of developing or accelerating the cementitious properties of cooperating cementitious material containing large proportions of available lime when incorporated therewith and formed by uniting at high heat lime and material rich in alumina-like material.

11. The high lime, cement material capable of developing'or accelerating the cementitious properties of cooperating cementitious material containing large proportions of available lime when incorporated there with and formed by uniting at high heat aluminous, material and earthy alkali material capable of uniting therewith.

12. The high lime, calcium aluminate, cement material capable of developing or accelerating the cementitious properties of 00- operating cementitious material containing large proportions of available lime when incorporated therewith and formed by uniting by calcination lime and high aluminous material containing iron and silica.

13. The high lime," calcium aluminate, cement material capable of developing or accelerating the cementitious properties of cooperating cementitious material containing large proportions of available lime when incorporated therewith and relatively high in alumina and low in silica formed by uniting lime and aluminous material containing iron or silica.

14. The high lime,'calcium aluminate, cement material capable of developing or accelerating the cementitious properties of cooperating cementitious material containing large proportions of available lime when incorporated therewith and containing about forty per cent. of alumina formed by uniting lime and high aluminous material.

15, The high'lime, calcium aluminate, cementmaterial'capable of developing or accelerating the cementitious properties of cooperating cementitious material containing large proportions of available lime when incorporated therewith and containing about forty per cent. of alumina formed by uniting at high heat lime and-bauxite.

16. The cement materialcapable of developing or accelerating the cementitious properties of cooperating cementitious material containing large proportions of available lime when incorporated therewith and comprising earthy alkali compounds relatively high in alumina-like material and low in silica formed by uniting large proportions of earthy alkali material with alumina-like material.

17. The high lime, calcium aluminate, cement materlal capable of developing or acceleratlng are cementitious properties of cooperating cementitious material containing large proportions of available lime when incorporated therewith, the lime being present in said cement material in amounts more than suflicient to be capable of combining in dicalcic proportions with the alumina in addition to combining with. any silica and other cooperating material. I v

18. The high lime, calcium aluminate, cement material capable of developing or accelerating the cementitious properties of cooperating cementitious material containing large proportions of'available lime when incorporated therewith and containing about forty per cent. of alumina.

19. The cement material capable of developing or accelerating the cementitious properties of cooperating cementitious material containing available lime when incorporated therewith, the lime being present in sald cement material in amounts more than sufiicient to be capable of combining in dicalcic proportions with the alumina in addition to combining with any silica and other cooperating material.

20. The cement material capable of developing or accelerating the cementitious Witnesses to the signature of Henry S.

Spackman:

HARRY L. DUNcAN, Jnssre B. KAY. Witnesses to the signature of Lazell:

WILLIAM P. WHITE, J OHN STROUD.

Ellis W.

EXTENSION OF PATENT.

Patent No. l, 029, 954.

Granted Jime18, 1912,10

HENRY: s. SPAGKMAN.

The above entitled patent has been extended, under the provisions of theAct of May 31, 1928, for five years, eleven months and twenty-four days from the expiration of the original term thereof.

- emanated April 26, 1930.

Commissioner of Patents.

celeratlng are cementitious properties of cooperating cementitious material containing large proportions of available lime when incorporated therewith, the lime being present in said cement material in amounts more than suflicient to be capable of combining in dicalcic proportions with the alumina in addition to combining with. any silica and other cooperating material. I v

18. The high lime, calcium aluminate, cement material capable of developing or accelerating the cementitious properties of cooperating cementitious material containing large proportions of'available lime when incorporated therewith and containing about forty per cent. of alumina.

19. The cement material capable of developing or accelerating the cementitious properties of cooperating cementitious material containing available lime when incorporated therewith, the lime being present in sald cement material in amounts more than sufiicient to be capable of combining in dicalcic proportions with the alumina in addition to combining with any silica and other cooperating material.

20. The cement material capable of developing or accelerating the cementitious properties of cooperating cementitious material containing large proportions ofavailable lime when incorporated therewith and comprising earthy alkali compounds relatively high in alumina-like material and low in silica.

HENRY S. SPACKMAN. ELLIS W. LAZELL.

Witnesses to the signature of Henry S.

Spackman:

HARRY L. DUNcAN, Jnssre B. KAY.

Witnesses to the signature of Lazell:

WILLIAM P. WHITE, J OHN STROUD.

Ellis W.

EXTENSION OF PATENT.

Patent No. l, 029, 954.

Granted Jime18, 1912,10

HENRY: s. SPAGKMAN.

The above entitled patent has been extended, under the provisions of theAct of May 31, 1928, for five years, eleven months and twenty-four days from the expiration of the original term thereof.

April 26, 1930.

Commissioner of Patents. 

